Solvolysis of other Organic Ligands

Solvolysis of other Organic Ligands.—A co-ordinated nitrile can be hydrolysed to a co-ordinated carboxamide  

For RCN = benzonitrile or 3- or 4-cyanophenol, this hydrolysis in aqueous solution is first-order in hydroxide-ion concentration. The rate enhancement due to the co-ordinated [Co(NHs)6] + moiety is ca. 10 times. The kinetic parameters for hydrolysis of these co-ordinated nitriles are listed in Table 2. A much greater rate enhancement, this time of at least 10 times, is reported for the mercury(n)-catalysed hy olyses of [Co(en)2 H2N(CH2) CN Br] +, where n = 1 or 2. The rates are first-order in mercury(n) concentration, but 

Kinetic parameters have been determined and discussed for copper(ii)-catalysed solvolyses of a range of terdentate (donor atoms ONS) and quadri-dentate (donor atoms OgNa) SchiflF-base complexes of nickel(n), in dimethyl sulphoxide. The rate law for solvolyses of substituted dithiocarbamato (Radtc) complexes of nickel(n) in the presence of added copper(n), in such solvents as dimethyl sulphoxide, dimethylacetamide, or acetone, is 

The ki and terms are assigned to dissociative and associative pathways respectively.  

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